Ab initio investigations on the HOSO2+O2→SO3+HO2 reaction

D. Majumdar, Gap Sue Kim, Jongseob Kim, Kyung Seek Oh, Jin Yong Lee, Kwang S. Kim, Won Yong Choi, Sung Hoon Lee, Myung Ho Kang, Byung Jin Mhin

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

HOSO2 radical is the key intermediate for the oxidation SO2 to SO3 by OH radical in the atmosphere. The structural aspects and the energetics of the reaction HOSO2+O2→SO3+HO2 have been studied using Møller-Plesset (MP2) and density functional (DFT) techniques with 6-31G** and triple-ζ, quadruple-ζ, and quintuple-ζ quality basis sets including diffuse basis functions. The detailed theoretical analyses have further revealed that this reaction could proceed through the formation of intermediate complexes and an intramolecular proton transfer like transition state. The energetics of these intermediate reactions has been studied in detail. The use of MP2 methods to study such radical mechanisms had some characteristic symmetry-breaking problem with larger basis sets. This unphysical situation with larger basis set MP2 calculations in this hypervalent system has been explained through the interpretation of the relevant energy surface.

Original languageEnglish
Pages (from-to)723-730
Number of pages8
JournalJournal of Chemical Physics
Volume112
Issue number2
DOIs
StatePublished - 8 Jan 2000

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